3,3-Dimethyl-1-(4-methylvaleryl)-cyclohexane perfume compositions

ABSTRACT

Compositions are described for the use in perfume and cologne of the compound  &lt;IMAGE&gt;   or of mixtures of the compounds  &lt;IMAGE&gt;  &lt;IMAGE&gt; &lt;IMAGE&gt;  to produce fruity, woody, piney aromas with armoise and floral nuances and slight chocolate undertones.

This application is a divisional of application for United StatesLetters Pat. Ser. No. 713,357, filed on Aug. 11, 1976, now U.S. Pat. No.4,062,894 issued on Dec. 13, 1977.

BACKGROUND OF THE INVENTION

The present invention relates to derivatives of1-acetyl-3,3-dimethylcyclohexane having the generic structure: ##STR3##wherein one of the dashed lines is a carbon-carbon single bond or acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and R is hydrogen or methyl, produced by thenovel process of our invention and novel compositions using one or moreof such 1-acetyl-3,3-dimethylcyclohexane derivatives to augment orenhance the flavor and/or aroma of consumable materials or impart flavorand/or aroma to consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply and to provide more uniform properties in the finishedproduct.

Sweet, fruity, raspberry, woody, lemon, piney, ionone-like, blueberryand floral aroma characteristics and sweet, raspberry, lemony, sweetfruity, red berry, piney, floral, ionone-like and nut meat flavorcharacteristics are particularly desirable for many uses in foodstuffflavorings, chewing gum flavors, toothpaste flavors and medicinalproduct flavors.

Fruity, woody, piney aromas with armoise and floral nuances and slightchocolate undertones are desirable in several types of perfumecompositions, perfumed articles and colognes.

Acetylcyclohexane and 1-acetyl-3,3-dimethylcyclohexane are knownsubstituents in perfumery. Thus, Arctander, "Perfume and FlavorChemicals (Aroma Chemicals)", published in 1969, disclosesacetylcyclohexane in Volume I, number 36:

"Peculiar camphoraceous-sweet odor with a certain amount of floraltones.

Although this chemical would primarily lend itself to perfumecompositions in the Pine, Wood, Herbaceous and other non-floral types,it has a similarity to the harsh-floral types such as Hyacinth, etc. andits sweetness is sometimes classified as "musky"."

1-Acetyl-3,3-dimethylcyclohexane is disclosed as a fragrance material inU.S. Pat. No. 3,487,102, issued on Dec. 30, 1969.

The fragrance properties of the aforementioned acetyldimethylcyclohexanederivatives are different in kind from the fragrance properties of thecompounds of the instant invention.

Firmenich's Dutch published application No. 7,500,838 discloses thepreparation of the compound having the structure: ##STR4## and disclosesits use in perfumery and in augmenting foodstuff flavors. The perfumeryuse of this compound and other members of its class as "floral, green,herbaceous and chypre" useful in galbanum resinoids is also disclosed.

The compounds disclosed in Dutch published application No. 7,500,838have organoleptic properties which causes them to be different in kindfrom the 1-acetyl-3,3-dimethylcyclohexane derivatives of our invention,which have unobvious, unexpected and advantageous characteristics in thefield of augmenting or enhancing the organoleptic impressions offoodstuffs, foodstuff flavors, perfumes, perfumed articles and medicinalproducts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the NMR spectrum for1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneproduced according to Example II.

FIG. 2 represents the Infrared spectrum for1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneproduced according to Example II.

FIG. 3 represents the GC-MS profile for 1-(3,3-dimethylcyclohexyl)-cisand trans-(2 and 3)-penten-1-one produced according to Example III.

FIG. 4 represents the NMR spectrum for 1-(3,3-dimethylcyclohexyl)-cisand trans-(2 and 3)-penten-1-one produced according to Example III.

FIG. 5 represents the Infrared spectrum for1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one producedaccording to Example III.

FIG. 6 represents the NMR spectrum for3,3-dimethyl-1-(4-methylvaleryl)-cyclohexane produced according toExample IV.

FIG. 7 represents the Infrared spectrum for3,3-dimethyl-1-(4-methylvaleryl)-cyclohexane produced according toExample IV.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having sweet, fruity, raspberry, woody, lemon,piney, ionone-like, blueberry and floral aroma characteristics andsweet, raspberry, lemony, sweet fruity, red berry, piney, floral,ionone-like and nut meat flavor characteristics and novel perfumecompositions, colognes and perfumed articles having fruity, woody, pineyaromas with armoise and floral nuances and slight chocolate undertones,may be provided by the utilization of one or more1-acetyl-3,3-dimethylcyclohexane derivatives having the formula:##STR5## wherein one of the dashed lines is a carbon-carbon single bondor a carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and R is hydrogen or methyl, in foodstuffs,chewing gums, toothpastes and medicinal product flavors.

The 1-acetyl-3,3-dimethylcyclohexane derivatives useful as indicatedsupra may be produced preferably by a process which comprises reactionof 1-acetyl-3,3-dimethylcyclohexane with an aldehyde having thestructure: ##STR6## thereby producing a compound having the structure:##STR7## wherein one of the dotted lines is a carbon-carbon double bondand the other of the dotted lines is a carbon-carbon single bond; in thepresence of an inorganic base or a mixture of boron oxide (B₂ O₃) andboric acid and utilizing the resulting product for its organolepticproperties or reducing the resulting product with hydrogen therebyproducing a compound having the structure: ##STR8## wherein R ishydrogen or methyl.

The first reaction with aldehyde having the structure: ##STR9## iscarried out at a temperature of from about 20° C up to 160° C, whenusing a catalyst which is an inorganic base, such as an alkali metalhydroxide, for example, potassium hydroxide, sodium hydroxide andlithium hydroxide or an alkaline earth metal hydroxide such as bariumhydroxide or lithium hydroxide; or at a temperature in the range of fromabout 100° C up to 200° C when using a catalyst which is a mixture ofboric acid (HBO₃) and boron oxide.

The time of reaction is inversely proportional to the temperature ofreaction. Thus, when using a mixture of boric acid and boron oxide thetime of reaction varies between 2 and 10 hours and when using a highertemperature the time of reaction varies from between 1 and 8 hours.

When using an inorganic base, the mole ratio of inorganicbase:1-acetyl-3,3-dimethylcyclohexane may vary from 0.1:1 up to 2:1 witha mole ratio of 1:1 being preferred. When using the mixture of boricacid and boron oxide the mole ratio of boronoxide:1-acetyl-3,3-dimethylcyclohexane varies from 0.5:1 up to 1.5:1with a mole ratio of 1:1 being preferred. The concentration of boricacid in the reaction mass may vary from 1 up to 80 grams per mole ofaldehyde having the structure: ##STR10##

In all cases, the mole ratio of aldehyde having the structure: ##STR11##may vary from 1:1 up to about 3:1 with a mole ratio of 2:1 beingpreferred.

Both reactions take place preferably in the presence of an inertsolvent.

The reduction reaction to form the genus having the structure ##STR12##is carried out preferably in the presence of inert solvents such asisopropyl alcohol; at hydrogenation pressures of between 50 and 150psig; at temperatures of between 25° and 150° C; and using hydrogenationcatalysts such as 5% palladiumon-carbon, rhodium, platinum and Raneynickel. The time of reaction varies inversely with the temperature andpressure of reaction. Thus, lower pressures and temperatures give riseto a need for greater times of reaction. Thus, the time of reaction mayvary from 1 hour up to 5 hours.

The previous reaction sequence is illustrated as follows: ##STR13##

Examples and organoleptic properties of materials produced according tothe aforementioned process are as follows:

                                      TABLE I                                     __________________________________________________________________________                                       ORGANOLEPTIC PROPERTIES                    NAME              STRUCTURE        FLAVOR         FRAGRANCE                   __________________________________________________________________________    Mixture of 1-(3,3-dimethyl- cyclohexyl)-4-methyl-cis-2- penten-1-one,         1-(3,3-dimethyl- cyclohexyl)-4-methyl-trans-2- penten-1-one, and 1-(3,3-      dimethylcyclohexyl)-4-methyl- 3-penten-1-one                                                     ##STR14##       Sweet, woody, raspberry, lemon, piney                                         aroma char- acter with sweet, rasp-                                           berry and lemon flavor character at                                           1.0 ppm.       Fruity woody, piney                                                           aroma with armoise,                                                           floral nuances and a                                                          slight chocolate                                                              undertone.                  Mixture of 1-(3,3-dimethyl- cyclohexyl)-cis-2-penten-1- one,                  1-(3,3-dimethylcyclo- hexyl)-trans-2-penten-1-one, and 1-(3,3-dimethylcycl    ohexyl)- 3-penten-1-one                                                                          ##STR15##       Sweet, raspberry, fruity, piney,                                              floral, ionone- like aroma with sweet,                                        weet fruity, raspberry, red berry,                                            piney, floral and ionone-like flavor                                          characteristics.                                                                             Sweet, fruity, woody                                                          (pine) with pine-                                                             apple-galbanum, hexalon                                                       notes.                      3,3-dimethyl-1- (4-methylvaleryl)- cyclohexane                                                   ##STR16##       Sweet, piney, fruity, blueberry, woody                                        aroma character with sweet, piney,                                            fruity, nut meat characteristics.                                                            Low-keyed, sweet,                                                             woody, somewhat choc-                                                         olate                       __________________________________________________________________________                                                      like.                   

When the 1-acetyl-3,3-dimethylcyclohexane derivatives of our inventionare used as food flavor adjuvants, the nature of the co-ingredientsincluded with each of the said 1-acetyl-3,3-dimethylcyclohexanederivatives in formulating the product composition will also serve toalter, modify, augment or enhance the organoleptic characteristics ofthe ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the 1-acetyl-3,3-dimethylcyclohexane derivative(s) of ourinvention, and in addition, sweetening agents which may be sugars,including sucrose or dextrose and/or artificial sweeteners such ascyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. it is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectines, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal,beta, beta-dimethylacrolein, methyl-n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methylfurfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2 -hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethylnaphthalene, dodecane, methyldiphenyl,methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, 1-phellandrene, p-cymene, 1-alphapinene; pyrazines suchas 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, and acetals (e.g.,1,1-diethoxy-ethane, 1,1-dimethoxy-ethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the1-acetyl-3,3-dimethylcyclohexane derivative(s) of our invention by notcovering or spoiling the organoleptic properties (aroma and/or taste)thereof; (ii) be non-reactive with the 1-acetyl-3,3-dimethylcyclohexanederivative(s) of our invention and (iii) be capable of providing anenvironment in which the 1-acetyl-3,3-dimethylcyclohexane derivative(s)can be dispersed or admixed to provide a homogeneous medium. Inaddition, selection of one or more flavoring adjuvants, as well as thequantities thereof will depend upon the precise organoleptic characterdesired in the finished product. Thus, in the case of flavoringcompositions, ingredient selection will vary in accordance with thefoodstuff, chewing gum, medicinal product or toothpaste to which theflavor and/or aroma are to be imparted, modified, altered or enhanced.In contradistinction, in the preparation of solid products, e.g.,simulated foodstuffs, ingredients capable of providing normally solidcompositions should be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of the1-acetyl-3,3-dimethylcyclohexane derivative(s) employed in a particularinstance can vary over a relatively wide range, depending upon thedesired organoleptic effects to be achieved. Thus, correspondingly,greater amounts would be necessary in those instances wherein theultimate food composition to be flavored is relatively bland to thetaste, whereas relatively minor quantities may suffice for purposes ofenhancing the composition merely deficient in natural flavor or aroma.The primary requirement is that the amount selected to be effective,i.e., sufficient to alter, modify or enhance the organolepticcharacteristics of the parent composition, whether foodstuff per se,chewing gum per se, medicinal product per se, toothpaste per se, orflavoring composition.

The use of insufficient quantities of the1-acetyl-3,3-dimethylcyclohexane derivative(s) will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavor-aroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantitites of the1-acetyl-3,3-dimethylcyclohexane derivative(s) ranging from a small buteffective amount, e.g., 0.5 parts per million up to about 100 parts permillion based on total composition are suitable. Concentrations inexcess of the maximum quantity stated are not normally recommended,since they fail to prove commensurate enhancement of organolepticproperties. In those instances, wherein a 1-acetyl-3,3-dimethylcyclohexane derivative is added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the 1-acetyl-3,3-dimethylcyclohexanederivative(s) in concentrations from about 0.1% up to about 15% byweight based on the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the 1-acetyl-3,3-dimethylcyclohexanederivative(s) with, for example, gum arabic, gum tragacanth, carrageenanand the like, and thereafter spray-drying the resultant mixture wherebyto obtain the particular solid product. Pre-prepared flavor mixes inpowder form, e.g., a fruit-flavored powder mix are obtained by mixingthe dried solid components, e.g., starch, sugar and the like and the1-acetyl-3,3-dimethylcyclohexane derivative(s) in a dry blender untilthe requisite degree of uniformity is achieved.

It is presently preferred to combine with the1-acetyl-3,3-dimethylcyclohexane derivative(s) of our invention, thefollowing adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl anthranilate;

5-Methylfurfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

Damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-one)

Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene)

Beta-cyclohomocitral (2,2,6-trimethyl-cyclohex-1-ene carboxaldehyde)

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl)-norbornadiene prepared according to ExampleII of U.S. Pat. No. 3,911,028, issued on Oct. 7, 1975.

The 1-acetyl-3,3-dimethylcyclohexane derivative(s) of our invention andone or more auxiliary perfume ingredients, including, for example,alcohols, aldehydes, nitriles, esters, cyclic esters and naturalessential oils, may be admixed so that the combined odors of theindividual components produce a pleasant and desired fragrance,particularly and preferably in rose fragrances. Such perfumecompositions usually contain (a) the main note or the "bouquet" orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low boiling fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the 1-acetyl-3,3-dimethylcyclohexane derivative(s) can be used toalter, modify or enhance the aroma characteristics of a perfumecomposition, for example, by utilizing or moderating the olfactoryreaction contributed by another ingredient in the composition.

The amount of 1-acetyl-3,3-dimethylcyclohexane derivative(s) of ourinvention which will be effective in perfume compositions as well as inperfumed articles and colognes depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.01%of a 1-acetyl-3,3-dimethylcyclohexane derivative(s) or even less (e.g.,0.005%) can be used to impart a fruity, woody, piney aroma with armoiseand floral nuances and slight chocolate undertones to soaps, cosmeticsor other products. The amount employed can range up to 70% of thefragrance components and will depend on considerations of cost, natureof the end product, the effect desired on the finished product and theparticular fragrance sought.

The 1-acetyl-3,3-dimethylcyclohexane derivative(s) of our invention isuseful [taken alone or together with other ingredients in perfumecompositions] as an olfactory component(s) in detergents and soaps,space odorants and deodorants, perfumes, colognes, toilet water, bathpreparations, such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations, such as creams, deodorants, hand lotions and sunscreens; powders, such as talcs, dusting powders, face powders and thelike. When used as (an) olfactory component(s) as little as 1% of1-acetyl-3,3-dimethylcyclohexane derivative(s) will suffice to impart anintense floral note to rose formulations. Generally, no more than 3% of1-acetyl-3,3-dimethylcyclohexane based on the ultimate end product, isrequired in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the1-acetyl-3,3-dimethylcyclohexane derivative(s). The vehicle can be aliquid such as an alcohol, a non-toxic alcohol, a non-toxic glycol, orthe like. The carrier can also be an absorbent solid, such as a gum(e.g., gum arabic) or components for encapsulating the composition (suchas gelatin).

It will thus be apparent that the 1-acetyl-3,3-dimethylcyclohexanederivative(s) of our invention can be utilized to alter, modify orenhance sensory properties, particularly organoleptic properties, suchas flavor(s) and/or fragrance(s) of a wide variety of consumablematerials.

The following Examples serve to illustrate our invention and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF 1-(3,3-DIMETHYLCYCLOHEXYL)-4-METHYL-CIS ANDTRANS-(2 and 3)-PENTEN-1-ONE

Reaction: ##STR17##

A solution of 474 grams of 1-acetyl-3,3-dimethylcyclohexane, 500 mlmethanol, 40 grams NaOH and 50 ml toluene is heated to reflux.Isobutyraldehyde (240 grams), is added dropwise over a 45 minute period.The reaction mixture is heated to reflux for a further 90 minutes, atwhich time, the solution is cooled to room temperature and neutralizedwith hydrochloric acid. The methanol is removed by distillation, and theaqueous layer is removed from the resulting two phase mixture. Theorganic layer is washed once with water and distilled rapidly through ashort column to afford a mixture of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-one(360 grams, 58%) [112°-117° C, 2.8 mm] and higher boiling productsidentified as: ##STR18##

Redistillation of this material through a 11/2 inch × 12 inch Goodloecolumn gave the following fractions:

    ______________________________________                                        Frac-                                                                         tion  Vapor Temp-                                                                              Liquid Temp-                                                                             Vacuum Weight                                                                              Reflux                               No.   erature (° C)                                                                     erature (° C)                                                                     mm Hg  (g)   Ratio                                ______________________________________                                        1     85-101     128        2.8     6.6  9:1                                  2     112        128        2.8    10.6  9:1                                  3     112        128        2.8    16.6  9:1                                  4     112        132        2.8    12.9  9:1                                  5     112        128        2.8    28.3  9:1                                  6     112        128        2.8    12.0  9:1                                  7     112        128        2.8    24.2  9:1                                  8     112        128        2.8    27.3  9:1                                  9     114        134        2.8    27.1  4:1                                  10    115        135        2.8    22.7  4:1                                  11    115        137        2.8    26.9  4:1                                  12    115        140        2.8    25.7  4:1                                  13    116        149        2.8    25.0  4:1                                  14    116        149        2.8    26.9  4:1                                  15    117        155        2.8    16.9  4:1                                  16    122        160        2.8    16.9  4:1                                  17    128        165        2.8    23.9  4:1                                  18    128        176        2.8    26.9  4:1                                  19    130        205        2.8    24.3  4:1                                  20    130        214        2.8    23.1  4:1                                  21    130        219        2.8    25.5  4:1                                  22    138        241        2.8    25.5  4:1                                  23    149        250        2.8    11.7  4:1                                  ______________________________________                                    

Fractions 5-13 contain greater than 99% desired product having theformulae: ##STR19##

The following fractions contain the following percentages of thismixture:

    ______________________________________                                        Fraction No.     Percent Desired Product                                      ______________________________________                                         3               60                                                            4               90                                                           5--13            > 99                                                         14               98                                                           15               96                                                           16               90                                                           17               60                                                           18               20                                                           ______________________________________                                    

Fractions 5-13, from a fragrance standpoint, have fruity, woody, pineyaromas with armoise, floral nuances and a slight chocolate undertone.

From a flavor standpoint, this material has a sweet, fruity, raspberry,woody, lemon, piney aroma with a sweet, raspberry and lemon flavorcharacter.

EXAMPLE II PREPARATION OF 1-(3,3-DIMETHYLCYCLOHEXYL)-4-METHYL-CIS ANDTRANS-(2 and 3)-PENTEN-1-ONE

Reaction: ##STR20##

A mixture of 1-acetyl-3,3-dimethylcyclohexane (462 grams),isobutyraldehyde (108 grams), boric acid (6.2 grams) and boron oxide (52grams) is heated and stirred in an autoclave at 150° C for 5 hours. Thesolution is filtered from inorganic salts and washed three times with10% HCl. Distillation affords 319 grams of1-acetyl-3,3-dimethylcyclohexane and 138 grams of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-one(22%, based on charged 1-acetyl-3,3-dimethylcyclohexane.

The 1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and3)-penten-1-one is determined by NMR and Infrared analyses to be amixture of: ##STR21##

The NMR spectrum for this mixture is set forth in FIG. 1. The Infraredspectrum for this mixture is set forth in FIG. 2.

The NMR analysis is as follows:

    ______________________________________                                        ppm                  Interpretation                                           ______________________________________                                        1.85 (s)                                                                      1.87 (s)             Methyl Groups "A"                                        2.62 (d, J = 1 H.sub.Z)                                                       2.76 (d, J = 1 H.sub.Z)                                                                            Methyl Groups "C"                                        2.03 (s)             Methyl Groups "B"                                        2.1 (s)                                                                       2.3-2.8 (broad multiplet)                                                                          H.sub.D                                                  3.14 (d, J = 7H.sub.Z)                                                                             CH.sub.2 Group "E"                                       5.28 (broad t, J = 7H.sub.Z)                                                                       H.sub.F                                                  6.0 and 6.28 (two multiplets)                                                                      H.sub.G                                                  6.68-6.92 (two multiplets)                                                                         H.sub.H                                                  ______________________________________                                    

The Infrared analysis is as follows:

    ______________________________________                                                 1665 cm.sup.-1                                                                1710                                                                          1690 (sh)     C═O                                                         1720 (sh)                                                                     1620 cm.sup.-1                                                                              C═C                                                ______________________________________                                    

EXAMPLE III SYNTHESIS OF 1-(3,3-DIMETHYLCYCLOHEXYL)-CIS AND TRANS-(2 and3)-PENTEN-1-ONE

Reaction: ##STR22##

A mixture of 462 grams of 1-acetyl-3,3-dimethylcyclohexane, 87 grams ofpropionaldehyde, 52 grams boron oxide and 6.2 grams or boric acid isheated at 150° C in an autoclave for 8 hours. After cooling to roomtemperature, the solution is filtered from inorganic salts, washed oncewith aqueous sodium carbonate and twice with saturated salt solution.Distillation through a short column afforded a mixture containing 367grams of 1-acetyl-3,3-dimethylcyclohexane and 60 grams of1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one (20%based on charged propionaldehyde).

A portion of the distillate rich in the desired product(s) was distilledthrough a 1.5 inch × 12 inch Goodloe column giving the followingfractions:

    ______________________________________                                        Frac-                                                                         tion  Vapor Temp-                                                                              Liquid Temp-                                                                             Vacuum Weight                                                                              Reflux                               No.   erature (° C)                                                                     erature (° C)                                                                     mm Hg  (g)   Ratio                                ______________________________________                                        1     55-52      105-103    2.5    10.2  9:1                                  2     52         109        2.2    11.1  9:1                                  3     60         126        2.0    5.5   9:1                                  4     82         138        2.0    6.6   4:1                                  5     88         138        2.0    3.0   4:1                                  6     90         140        2.0    5.3   4:1                                  7     90         140        2.0    6.7   4:1                                  8     90         144        2.0    6.7   4:1                                  9     90         154        2.0    6.5   4:1                                  10    95         181        2.0    7.0   4:1                                  11    93         220        2.0    2.6   4:1                                  ______________________________________                                    

Fraction #7, at 2 ppm, has a sweet, raspberry, fruity, piney, floral,ionone aroma and a sweet, sweet fruity, redberry, raspberry, piney,floral, ionone-like flavor. The mixture 1-(3,3-dimethylcyclohexyl)-cisand trans-(2 and 3)-penten-1-one is trapped out via preparative GLC andhas the structure: ##STR23##

The GC-MS profile for this mixture is set forth in FIG. 3. The NMRspectrum is set forth in FIG. 4. The Infrared spectrum is set forth inFIG. 5.

The NMR analysis is as follows:

    ______________________________________                                        δ ppm          Interpretation                                           ______________________________________                                        1.95 (s, 6H)         CH.sub.3 Groups "A"                                      2.08 (t, 3, J = 8H.sub.Z)                                                                          CH.sub.3 Groups "B"                                      2.25 (quintet, 2H, J = 8H.sub.Z)                                                                   CH.sub.2 Groups "C"                                      2.7-2.9 (broad multiplet,                                                                          H.sub.D                                                  1H)                                                                           6.05 and 6.22 (two multiplets)                                                                     H.sub.E                                                  6.75-7.05 (m, 1H)    H.sub.F                                                  ______________________________________                                    

The Infrared analysis is as follows: C═O 1665 and 1685 cm⁻¹ C═C 1620

EXAMPLE IV HYDROGENATION OF 1-(3,3-DIMETHYLCYCLOHEXYL)-4-METHYL-CIS ANDTRANS-(2 and 3)-PENTEN-1-ONE

Reaction: ##STR24##

Into a 250 cc Parr shaker is placed 107 grams of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneprepared according to Example I, 1 gram of 5% Palladium-on-carboncatalyst and 125 grams of isopropyl alcohol. The Parr shaker is sealedand heated to a temperature of 125° C at a pressure of 50-150 psig ofhydrogen and maintained at that pressure range and temperature range fora period of 1.5 hours. At the end of the 1.5 hour period, the reactionproduct is filtered and distilled in a 48 inch Vigreaux column. Thedistillation data is as follows:

    ______________________________________                                        Frac-                                                                         tion  Vapor Temp-                                                                              Liquid Temp-                                                                             Vacuum Weight                                                                              Reflux                               No.   erature (° C)                                                                     erature (° C)                                                                     mm Hg  (g)   Ratio                                ______________________________________                                        1     67-89      118-126    2.2    3.8   9:1                                  2     91         137        2.2    3.7   9:1                                  3     91         129        2.2    7.4   4:1                                  4     91         129        2.2    8.6   4:1                                  5     91         129        2.2    13.4  4:1                                  6     91         129        2.2    14.0  4:1                                  7     91         131        2.2    15.2  4:1                                  8     91         156        2.2    14.7  4:1                                  9     94         187        2.2    8.2   4:1                                  10    98         240        2.2    3.5   4:1                                  ______________________________________                                    

From a food flavor standpoint, fraction #6, resulting from thedistillation, has a sweet, piney, fruity, blueberry, woody aroma with asweet, piney, fruity, nut-meat flavor character.

From a perfumery standpoint, bulked fractions #2-9, at 10% in food gradealcohol, have a low-keyed, sweet woody aroma with chocolate-likenuances.

Fraction #7 is determined by NMR, Infrared and Mass Spectral analyses tohave the structure: ##STR25##

The NMR analysis is as follows:

    ______________________________________                                        δ ppm          Interpretation                                           ______________________________________                                        0.82-0.98 (m, 12H)   CH.sub.3 Groups                                          2.43 (t, 2H, J = 8H.sub.Z)                                                                         Methylene "A"                                            ______________________________________                                    

The Infrared analysis is as follows:

2950 cm⁻¹

2870

1700

1560 (C=O)

1390

1360

the Mass Spectral analysis is as follows: 111, 41, 43, 69, 55 and 27

The NMR spectrum for this compound is set forth in FIG. 6. The Infraredspectrum for this compound is set forth in FIG. 7.

EXAMPLE V RASPBERRY FLAVOR FORMULATION

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Vanillin             2.0                                                      Maltol               5.0                                                      Parahydroxybenzylacetone                                                                           5.0                                                      Alpha-ionone (10% in propylene glycol)                                                             2.0                                                      Ethyl butyrate       6.0                                                      Ethyl acetate        16.0                                                     Dimethyl sulfide     1.0                                                      Isobutyl acetate     13.0                                                     Acetic acid          10.0                                                     Acetaldehyde         10.0                                                     Propylene glycol     930.0                                                    ______________________________________                                    

1-(3,3-Dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneprepared according to Example I is added to half of the aboveformulation at the rate of 2.0%. The formulation with the1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneis compared with the formulation without the1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneat the rate of 0.01 percent (100 ppm) in water and evaluated by a benchpanel.

The flavor containing the 1-(3,3-dimethylcyclohexyl)-4-methyl-cis andtrans-(2 and 3)-penten-1-one is found to have substantially sweeteraroma notes and a sweet raspberry, raspbery kernel-like and sweetaftertaste and mouthfeel missing in the basic raspberry formulation. Itis the unanimous opinion of the bench panel that the chemical,1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-onerounds the flavor out and contributes to a very natural fresh aroma andtaste as found in full ripe raspberries. Accordingly, the flavor withthe addition of the 1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2and 3)-penten-1-one is considered as substantially better than theflavor without 1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and3)-penten-1-one.

EXAMPLE VI RASPBERRY FLAVOR FORMULATION

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Vanillin             2.0                                                      Maltol               5.0                                                      Parahydroxybenzylacetone                                                                           5.0                                                      Alpha-ionone (10% in propylene glycol)                                                             2.0                                                      Ethyl butyrate       6.0                                                      Ethyl acetate        16.0                                                     Dimethyl sulfide     1.0                                                      Isobutyl acetate     13.0                                                     Acetic acid          10.0                                                     Acetaldehyde         10.0                                                     Propylene glycol     930.0                                                    ______________________________________                                    

1-(3,3-Dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one preparedaccording to Example III is added to half of the above formulation atthe rate of 2.0%. The formulation with the1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one iscompared with the formulation without the 1-(3,3-dimethylcyclohexyl)-cisand trans-(2 and 3)-penten-1-one at the rate of 0.01 percent (100 ppm)in water and evaluated by a bench panel.

The flavor containing the 1-(3,3-dimethylcyclohexyl)-cis and trans-(2and 3)-penten-1-one is found to have substantially sweeter aroma notesand a sweet raspberry, raspberry kernel-like and sweet aftertaste andmouthfeel missing in the basic raspberry formulation. It is theunanimous opinion of the bench panel that the chemical,1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one roundsthe flavor out and contributes to a very natural fresh aroma and tasteas found in full ripe raspberries. Accordingly, the flavor with theaddition of the 1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and3)-penten-1-one is considered as substantially better than the flavorwithout 1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one.

EXAMPLE VII A. POWDER FLAVOR COMPOSITION

20 Grams of the flavor composition of Example V is emulsified in asolution containing 300 grams gum acacia and 700 grams water. Theemulsion is spray-dried with a Bowen Lab Model Drier utilizing 260c.f.m. of air with an inlet temperature of 500° F., an outlettemperature of 200° F., and a wheel speed of 50,000 r.p.m.

B. SUSTAINED RELEASE FLAVOR

The following mixture is prepared:

    ______________________________________                                        Ingredient             Parts by Weight                                        ______________________________________                                        Liquid Raspberry Flavor                                                       Composition of Example V                                                                             20                                                     Propylene glycol       9                                                      Cab-O-Sil®M-5                                                             (Brand of Silica produced by the                                              Cabot Corporation of 125 High                                                 Street, Boston, Mass. 02110;                                                  Physical Properties:                                                           Surface Area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu.ft.)                                                                            5.00                                                   ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid raspberry flavor composition ofExample V with vigorous stirring, thereby resulting in a viscous liquid.71 Parts by weight of the powder flavor composition of Part A, supra, isthen blended into the said viscous liquid, with stirring at 25° C for aperiod of 30 minutes resulting in a dry, free flowing sustained releaseflavor powder.

EXAMPLE VIII

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of ExampleVI is added to the solution which is then homogenized to form anemulsion having particle size typically in the range of 2-5 microns.This material is kept at 120° F. under which conditions the gelatin willnot jell.

Coascervation is induced by adding, slowly and uniformly 40 parts byweight of a 20% aqueous solution of sodium sulphate. Duringcoascervation, the gelatin molecules are deposited uniformly about eachoil droplet as a nucleus.

Gelation is effected by pouring the heated coascervate mixture into1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65°F. The resulting jelled coascervate may be filtered and washed withwater at temperatures below the melting point of gelatin, to remove thesalt.

Hardening of the filtered cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove residual formaldehyde.

EXAMPLE IX CHEWING GUM

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example VII. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long lastingraspberry flavor.

EXAMPLE X CHEWING GUM

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example VIII. 300 Parts of sucroseand 100 parts of corn syrup are then added. Mixing is effected in aribbon blender with jacketed side walls of the type manufactured by theBaker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long lastingraspberry flavor.

EXAMPLE XI TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight   Ingredient                                                  ______________________________________                                        Group "A"                                                                     30.200            Glycerin                                                    15.325            Distilled water                                              .100             Sodium benzoate                                              .125             Saccharin sodium                                             .400             Stannous fluoride                                           Group "B"                                                                     12.500            Calcium carbonate                                           37.200            Dicalcium phosphate                                                           (Dihydrate)                                                 Group "C"                                                                     2.000             Sodium N-Lauroyl                                                              Sarcosinate (foaming                                                          agent)                                                      Group "D"                                                                     1.200             Flavor Material of                                                            Example VII                                                 100.00 (Total)                                                                ______________________________________                                    

The resulting toothpaste when used in a normal toothbrushing procedureyields a pleasant raspberry flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XII CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example VIII isadded to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich Chewable Vitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                                                Gms/1000 -tablets                                     ______________________________________                                        Vitamin C (ascorbic acid)                                                                              70.0                                                 as ascorbic acid-sodium ascorbate mixture 1:1                                 Vitamin B.sub.1 (thiamine mononitrate)                                        as Rocoat® thiamine mononitrate 1/3%                                      (Hoffman La Roche)       4.0                                                  Vitamin B.sub.2 (riboflavin)                                                  as Rocoat® riboflavin 1/390                                                                        5.0                                                  Vitmain B.sub.6 (pyridoxine hydrochloride)                                    as Rocoat® pyridoxine hydrochloride 1/390                                                          4.0                                                  Niacinamide                                                                   as Rocoat® niacinamide 1/3%                                                                        33.0                                                 Calcium pantothenate     11.5                                                 Vitamin B.sub.12 (cyanocobalamin)                                             as Merck 0.1% in gelatin 3.5                                                  Vitamin E (dl-alpha tocopheryl acetate)                                       as dry Vitamin E acetate 1/390 Roche                                                                   6.6                                                  d-Biotin                 0.044                                                Certified lake color     5.0                                                  Flavor of Example XXVIII (as indicated                                                                 above                                                Sweetener - sodium saccharin                                                                           1.0                                                  Magnesium stearate lubricant                                                                           10.0                                                 Mannitol q.s. to make    500.0                                                ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong raspberry flavor for a period of 12 minutes.

EXAMPLE XIII BLUEBERRY FONDANT FORMULATION

The following blueberry fondant formulation is prepared:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Oil of Cardamom      0.25                                                     Oil of Cloves        0.50                                                     Oil of Galanga       1.00                                                     Oil of Cinnamon      1.25                                                     Oil of Coriander     2.50                                                     Oil of Fennel        2.50                                                     Amyl Acetate         22.00                                                    Benzyl Benzoate      33.00                                                    1-(3,3-dimethylcyclo-                                                                              37.00                                                    hexyl)-4-methyl-cis                                                           and trans-(2 and 3)-                                                          penten-1-one, fraction                                                        #6 produced according                                                         to Example IV        0.1                                                      ______________________________________                                    

The 1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and3)-penten-1-one produced according to Example V adds sweet, piney,fruity and woody nuances to the blueberry fondant formulation therebycausing it to be more natural-like in taste and aroma.

EXAMPLE XIV

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient            Amount (Grams)                                          ______________________________________                                        n-Decyl Aldehyde       1                                                      n-Dodecyl Aldehyde     2                                                      Methyl Nonyl Acetaldehyde                                                                           0.5                                                     Linalool              50                                                      Linalyl Acetate       70                                                      Phenyl Ethyl Alcohol  100                                                     Petigrain SA          20                                                      Bergamot Oil          30                                                      Alpha Methyl Ionone   25                                                      1-(3,3-dimethylcyclo-                                                         hexyl)-4-methyl-cis and                                                       trans-(2 and 3)-penten-1-                                                     one produced according to                                                                           10                                                      Example II                                                                    Cyclized Bicyclo C-12 material                                                produced according to the                                                     process of Example IV of                                                      Canadian Patent 854,225,                                                      issued on October 20, 1970                                                                           5                                                      Isobornyl cyclohexyl alcohol                                                                        10                                                      Benzyl Acetate        25                                                      2-n-Heptylcyclopentanone                                                                             5                                                                            353.3 (TOTAL)                                           ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel natural amber quality. This basecomposition can be admixed with aqueous ethanol, chilled and filtered toproduce a finished cologne. The cologne so prepared has an amber aromaleaning towards a woody amber note with an excellent armoise nuance. Thebase composition can also be used to scent soap or other toilet goodssuch as lotion, aerosol, sprays and the like.

EXAMPLE XV PREPARATION OF A COSMETIC-POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of 1-(3,3-dimethylcyclohexyl)-4-methyl-cis andtrans-(2 and 3)-penten-1-one prepared according to Example II. It has anexcellent piney, woody, floral and fruity aroma.

EXAMPLE XVI PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976) with a piney, woody odor are prepared containing 0.10%,0.15% and 0.20% of 1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2and 3)-penten-1-one prepared according to Example II. They are preparedby adding and homogeneously mixing the appropriate quantity of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-onein the liquid detergent. The detergents all possess a piney, woodyfragrance, the intensity increasing with greater concentrations of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and3)-penten-1-one.

EXAMPLE XVII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

1-(3,3-Dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneprepared according to the process of Example II is incorporated in acologne at a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).A distinct and definite piney, woody fragrance is imparted to thecologne and to the handkerchief perfume.

EXAMPLE XVIII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition of Example XIV is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-onein the composition of Example II affords a distinct and definite strongamber aroma with piney, woody notes to the handkerchief perfume andcologne.

EXAMPLE XIX PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram of1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneof Example II until a substantially homogeneous composition is obtained.The perfumed soap composition manifests an excellent woody, piney aroma.

EXAMPLE XX PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder (Lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) is mixed with 0.15 g of the1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-oneof Example II until a substantially homogeneous composition is obtained.This composition has an excellent woody, piney aroma.

What is claimed is:
 1. The perfume composition comprising the compound with the structure: ##STR26## and one or more auxiliary perfume ingredients.
 2. The perfume composition comprising a mixture of 1-(3,3-dimethylcyclohexyl)-4-methyl-cis-2-penten-1-one, 1-(3,3-dimethylcyclohexyl)-4-methyl-trans-2-penten-1-one, and 1-(3,3-dimethylcyclohexyl)-4-methyl-3-penten-1-one, and one or more auxiliary perfume ingredients.
 3. The cologne composition comprising ethanol, water and the compound with the structure: ##STR27##
 4. The cologne composition comprising ethanol, water and a mixture of 1-(3,3-dimethylcyclohexyl)-4-methyl-cis-2-penten-1-one, 1-(3,3-dimethylcyclohexyl)-4-methyl-trans-2-penten-1-one, and 1-(3,3-dimethylcyclohexyl)-4-methyl-3-penten-1-one. 